Studies of carotenoid one-electron reduction radicals.

The relative reduction potentials of a variety of carotenoids have been established by monitoring the reaction of carotenoid radical anion (CAR1(*-)) with another carotenoid (CAR2) in hexane and benzene. This order is consistent with the reactivities of the carotenoid radical anions with porphyrins and oxygen in hexane. In addition, investigation of the reactions of carotenoids with reducing radicals in aqueous 2% Triton-X 100, such as carbon dioxide radical anion (CO2(*-)), acetone ketyl radical (AC(*-)) and the corresponding neutral radical (ACH(*)), reveals that the reduction potentials for beta-carotene and zeaxanthin lie in the range -1950 to -2100 mV and those for astaxanthin, canthaxanthin and beta-apo-8'-carotenal are more positive than -1450 mV. This illustrates that the presence of a carbonyl group causes the reducing ability to decrease. The radical cations have been previously shown to be strong oxidising agents and we now show that the radical anions are very strong reducing agents.